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US20020072622A1 - Preparation of oxirane compounds - Google Patents

Preparation of oxirane compounds Download PDF

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Publication number
US20020072622A1
US20020072622A1 US09/736,522 US73652200A US2002072622A1 US 20020072622 A1 US20020072622 A1 US 20020072622A1 US 73652200 A US73652200 A US 73652200A US 2002072622 A1 US2002072622 A1 US 2002072622A1
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Prior art keywords
alkylaryl
oxirane
catalyst
compound
hydroperoxide
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US6455712B1 (en
Inventor
Garo Vaporciyan
Brendan Murray
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Shell USA Inc
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Individual
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Priority to US09/736,522 priority Critical patent/US6455712B1/en
Application filed by Individual filed Critical Individual
Priority to TW090130947A priority patent/TWI248929B/en
Priority to TW090130929A priority patent/TWI247743B/en
Priority to CNB01820578XA priority patent/CN1213041C/en
Priority to EP01270532A priority patent/EP1347962A2/en
Priority to CNB018205771A priority patent/CN1232516C/en
Priority to AU2002217114A priority patent/AU2002217114B2/en
Priority to BR0116101-6A priority patent/BR0116101A/en
Priority to AU2002216112A priority patent/AU2002216112B2/en
Priority to RU2003121243/04A priority patent/RU2282624C2/en
Priority to PCT/EP2001/014751 priority patent/WO2002048127A2/en
Priority to PCT/EP2001/014748 priority patent/WO2002048125A2/en
Priority to RU2003121244/04A priority patent/RU2282625C2/en
Priority to AU3843302A priority patent/AU3843302A/en
Priority to RU2003121245/04A priority patent/RU2282623C2/en
Priority to BR0116099-0A priority patent/BR0116099A/en
Priority to KR10-2003-7007771A priority patent/KR20030075151A/en
Priority to EP01270533A priority patent/EP1366031A2/en
Priority to JP2002549656A priority patent/JP2004517841A/en
Priority to JP2002549657A priority patent/JP2004517842A/en
Priority to EP01986878A priority patent/EP1343776A2/en
Priority to KR10-2003-7007769A priority patent/KR20030059334A/en
Priority to JP2002549658A priority patent/JP2004525870A/en
Priority to KR1020037007770A priority patent/KR100843780B1/en
Priority to AU1711402A priority patent/AU1711402A/en
Priority to BR0116100-8A priority patent/BR0116100A/en
Priority to PCT/EP2001/014750 priority patent/WO2002048126A2/en
Priority to TW090130928A priority patent/TW593298B/en
Priority to AU2002238433A priority patent/AU2002238433B2/en
Priority to AU1611202A priority patent/AU1611202A/en
Priority to CNB018205909A priority patent/CN1243743C/en
Publication of US20020072622A1 publication Critical patent/US20020072622A1/en
Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VAPORCIYAN, GARO GARBIS, MURRIA, BRENDAN DERMOT
Assigned to SHELL OIL COMPANY reassignment SHELL OIL COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BYERS, DALLAS LEA, MEYER, CHARLES LEE, SALANITRO, JOSEPH PATRICK, SUN, PAUL TA-CHIN
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides

Definitions

  • the present invention relates to a process for the preparation of oxirane compounds.
  • NL-C-1010372 describes a process comprising reacting propene with ethylbenzene hydroperoxide to obtain propylene oxide and 1-phenyl ethanol. The 1-phenyl ethanol is subsequently dehydrated to obtain styrene, which is a useful starting material for other chemical reactions.
  • NL-C-1012749 describes a similar process in which propene is reacted with cumenehydroperoxide to obtain propene oxide and 2-phenyl-2-propanol. The latter is described to be subsequently dehydrated into alpha-methylstyrene which is described to be an industrially applicable compound.
  • Suitable outlets can often be found for many of the products co-produced in the prior art processes for manufacturing oxirane compounds such as propylene oxide. However, it can be beneficial to be able to produce solely the oxirane compounds such as propylene oxide.
  • EP-B-609455 a process is described for producing cresol by (1) oxidation of cymene to obtain a solution of oxygenation products containing tertiary hydroperoxide and primary hydroperoxide, (2) reduction of the content of primary hydroperoxide, (3) decomposition of the reaction mixture to obtain cresol and some by-products, and (4) subjecting the decomposition mixture to hydrogenation to convert part of the by-products to cymene and/or cresol.
  • EPB-609455 solely relates to the preparation of cresol.
  • the present invention relates to a process for the preparation of oxirane compounds, which process comprises:
  • step (ii) contacting at least a part of the alkylaryl hydroperoxide obtained in step (i) with an olefin in the presence of a catalyst to obtain a product stream comprising an oxirane compound and alkylaryl hydroxyl,
  • step (iii) optionally reacting part of the alkylaryl hydroperoxide obtained in step (i) to obtain a mixture comprising (a) phenol, and (b)a ketone and/or aldehyde, and optionally (c) by-products,
  • step (iv) separating oxirane compound from the product stream of step (ii)to obtain (a) a residual product stream and (b) oxirane,
  • step (v) contacting at least a part of the residual product stream with hydrogen to obtain alkylaryl, wherein at least a part of said alkylaryl is recycled to step (i).
  • ethylbenzene is the alkylaryl compound most widely used in the preparation of an oxirane compound at present, it has been found that process step (i) can be carried out at higher conversion and higher selectivity if the alkylaryl compound employed is an alkylbenzene in which the alkyl substituent is a branched alkyl substituent comprising from 3 to 10 carbon atoms.
  • a more preferred alkylaryl compound contains 1 or 2 alkyl substituents.
  • An alkylaryl compound containing several substituents has the advantage that it can contain several hydroperoxide groups. However, in view of potential side-reactions, it is preferred that there are no more than 3 substituents, more preferably no more than 2 substituents.
  • the alkylaryl compound is cumene and/or di(iso-propyl)benzene.
  • a single type of compound is preferred in order to be able to optimise the process conditions for this specific compound.
  • the oxidation of the alkylaryl can be carried out by any suitable process known in the art.
  • the oxidation can be carried out in the liquid phase in the presence of a diluent.
  • This diluent is preferably a compound which is liquid under the reaction conditions and does not react with the starting materials and product obtained.
  • the diluent can also be a compound necessarily present during the reaction. For example, if the alkylaryl is cumene the diluent can be cumene as well.
  • step (i) The product obtained in step (i) can be used as such in step (ii), or it can be preferred to separate off some compounds, or it can be preferred to only use part of the product obtained and to use another part in another process.
  • step (iii) part of the product of step (i) is used in step (iii), namely reaction of the alkylaryl hydroperoxide to obtain phenol and ketone and/or aldehyde.
  • the phenol obtained can contain substituents.
  • the reaction of the alkylaryl hydroperoxide can be attained by contacting the alkylaryl hydroperoxide with a catalyst such as an acidic catalyst.
  • the acidic catalysts which can be used include, but not limited to, sulphuric acid, hydrochloric acid, perchloric acid, sulphur dioxide and sulphur trioxide; organic acids such as benzenesulphonic acid, p-toluenesulphonic acid, cresolsulphonic acid and chloroacetic acid; solid acids such as silica-alumina, alumina and acidic ion exchange resins; heteropolyacids such as tungstosilicic acid, tungstophosphoric acid and molybdophosphosphoric acid.
  • sulphuric acid and/or cresolsulphonic acid are used.
  • the amount of catalyst to be used is usually in the range of from about 0.0001 to 1% wt, based on the reaction mixture to be treated.
  • the reaction temperature is usually in the range of from 30 to 150° C.
  • the alkylaryl hydroperoxide can be subject to the reaction after other compounds have been separated off from the reaction product of step (i). However, it is preferred to subject part of the reaction product of step (i) directly to the reaction of step (iii).
  • step (iii) usually produces by-products.
  • the desired products can be separated from the reaction product of step (iii) and at least part of the by-products obtained in step (iii) are sent to step (v).
  • Product to be hydrogenated can be separated off and subsequently subjected to hydrogenation, or part or all of the remaining reaction product can be directly subjected to hydrogenation.
  • step (iii) If part of the alkylaryl hydroperoxide is converted into phenol and ketone and/or aldehyde, it is preferred that the alkylaryl is cumene as this gives phenol and acetone in step (iii).
  • step (ii) alkylaryl hydroperoxide obtained in step (i) is contacted with olefin in the presence of a catalyst to obtain an oxirane compound and hydroxyalkylaryl.
  • a catalyst which can suitably used in such process comprises titanium on silica and/or silicate.
  • a preferred catalyst is described in EP-B-345856, the disclosure of which is herein incorporated by reference.
  • the reaction generally proceeds at moderate temperatures and pressures, in particular at temperatures in the range of from 0 to 200° C., preferably in the range from 25 to 200° C.
  • the precise pressure is not critical as long as it suffices to maintain the reaction mixture in a liquid condition. Atmospheric pressure may be satisfactory. In general, pressures can be in the range of from about 1 to about 100 ⁇ 10 5 N/m 2 .
  • the olefin to be used in the process in the present invention depends on the oxirane compound to be prepared.
  • the olefin contains from 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms.
  • the olefin is propene.
  • the liquid mixture comprising the desired products is separated from the catalyst.
  • the oxirane compound can then be separated from the reaction product in any way known to be suitable to someone skilled in the art.
  • the liquid reaction product may be worked up by fractional distillation, selective extraction and/or filtration.
  • the catalyst, any solvent which might be present and any unreacted olefin or alkylaryl hydroperoxide may be recycled for further utilization.
  • Process step (ii) can be carried out with the catalyst in the form of a slurry, of a moving bed or a fluidized bed.
  • a fixed bed is preferred for large-scale industrial application.
  • the process may be carried out in a batch-wise manner, semi-continuously or continuously.
  • the liquid containing the reactants may then be passed through the catalyst bed, so that the effluent from the reaction zone is substantially free from catalyst.
  • a hydrogenation treatment which can be used comprises contacting reaction product with hydrogen at a temperature of from about 140 to about 330° C., preferably of from about 180 to about 320° C., and a pressure of from about 0.1 to about 10 ⁇ 10 5 N/m 2 .
  • the hydrogenation treatment is preferably carried out in the presence of a hydrogenation catalyst.
  • the hydrogenation catalyst will contain a metal on a solid carrier which metal catalyses hydrogenation.
  • Preferred catalysts are catalysts containing from 0.5 to 5% wt of metal or a metal compound on a carrier.
  • the metal present as metal or metal compound is one or more metal chosen from Group 1b, 2b, 3a, 4a, 4b, 5b, 6b, 7b and 8 of the Periodic Table of the Elements described in the Handbook of Chemistry and Physics, 63rd Edition.
  • Catalysts which have been found to be suitable are the catalysts described in U.S. Pat. No. 5,475,159, the description of which is herein incorporated by reference. Further preferred catalyst are described in PCT/EP99/04275, the description of which is herein incorporated by reference.
  • the hydrogenated product can be recycled in total or in part. If only part of the hydrogenated product is recycled, the desired fraction can be separated off in any way suitable to someone skilled in the art.
  • the epoxidation catalyst was a catalyst containing titanium on silica which was prepared as described in the Example according to the teaching of EP-A-345856, the description of which is herein incorporated by reference.
  • the hydrogenation catalyst was a catalyst containing copper, zinc and zirconium prepared according to Example 3 of U.S. Pat No. 5,475,159, incorporated herein by reference.
  • a reaction mixture containing about 6 mole of 1-octene per mole of cumene hydroperoxide was fed to a reactor containing the fresh epoxidation catalyst described above at a temperature of 40° C. Octene oxide was separated off. It was found that 55% wt of 1-octene was converted into octene oxide.
  • a mixture containing 17% wt of 2-phenyl-2-propanol and 83% wt of cumene was contacted with hydrogen in the presence of the hydrogenation catalyst described above at a temperature of 140° C. and a pressure of 20 ⁇ 10 5 N/m 2 during 2 hours.
  • the product obtained contained 10% wt of 2-phenyl-2-propanol, 86% wt of cumene, and 4% wt of alpha methyl styrene.
  • a mixture containing 17% wt of 2-phenyl-2-propanol and 83% wt of cumene was contacted with hydrogen in the presence of a hydrogenation catalyst comprising 5% wt of palladium on a charcoal carrier, at a temperature of 225° C. and a pressure of 20 ⁇ 10 5 N/m 2 during 2 hours.
  • the product obtained contained 1 % wt of 2-phenyl-2-propanol, 94% wt of cumene, 3% wt of i-propylcyclohexane and 2% wt of further compounds.
  • Example 2 The experiment of Example 2 was repeated with the difference that the temperature was 280° C.
  • the product obtained contained no 2-phenyl-2-propanol, 89 % wt of cumene, 10% wt of i-propylcyclohexane and 1 % wt of further compounds.
  • a reaction mixture containing about 6 mole of 1-octene per mole of ethylbenzene hydroperoxide was fed to a reactor containing the fresh epoxidation catalyst described in Example 1 at a temperature of 40° C. Octene oxide was separated off. It was found that 41% wt of 1-octene was converted into octene oxide.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A process for preparing oxirane compounds, which process comprises:
(i) oxidizing an alkylaryl to obtain a stream comprising alkylaryl hydroperoxide,
(ii) contacting at least a part of the alkylaryl hydroperoxide obtained in step (i) with an olefin in the presence of a catalyst to obtain a product stream comprising an oxirane compound and alkylaryl hydroxyl,
(iii) optionally reacting part of the alkylaryl hydroperoxide obtained in step (i) to obtain a mixture comprising (a) phenol, and (b) a ketone and/or aldehyde,and (c) optionally by-products,
(iv) separating oxirane compound from the product stream of step (ii) to obtain (a) a residual product stream and (b) oxirane, and
(v) contacting at least a part of the residual product stream with hydrogen to obtain alkylaryl, wherein at least a part of said alkylaryl is recycled to step (i).

Description

    BACKGROUND OF THE INVENTION
  • The present invention relates to a process for the preparation of oxirane compounds. [0001]
  • Processes for preparing oxirane compounds such as propylene oxide are well known. NL-C-1010372 describes a process comprising reacting propene with ethylbenzene hydroperoxide to obtain propylene oxide and 1-phenyl ethanol. The 1-phenyl ethanol is subsequently dehydrated to obtain styrene, which is a useful starting material for other chemical reactions. NL-C-1012749 describes a similar process in which propene is reacted with cumenehydroperoxide to obtain propene oxide and 2-phenyl-2-propanol. The latter is described to be subsequently dehydrated into alpha-methylstyrene which is described to be an industrially applicable compound. [0002]
  • Suitable outlets can often be found for many of the products co-produced in the prior art processes for manufacturing oxirane compounds such as propylene oxide. However, it can be beneficial to be able to produce solely the oxirane compounds such as propylene oxide. [0003]
  • In EP-B-609455, a process is described for producing cresol by (1) oxidation of cymene to obtain a solution of oxygenation products containing tertiary hydroperoxide and primary hydroperoxide, (2) reduction of the content of primary hydroperoxide, (3) decomposition of the reaction mixture to obtain cresol and some by-products, and (4) subjecting the decomposition mixture to hydrogenation to convert part of the by-products to cymene and/or cresol. EPB-609455 solely relates to the preparation of cresol. [0004]
  • A process has now been found which makes it possible to prepare oxirane compounds without the need to prepare further compounds at the same time. Although some of the process steps of the process according to the present invention are known per se, there is no teaching or hint in the prior art to combine these process steps in this particular way. [0005]
    • SUMMARY OF THE INVENTION
  • The present invention relates to a process for the preparation of oxirane compounds, which process comprises: [0006]
  • (i) oxidizing an alkylaryl to obtain a stream comprising alkylaryl hydroperoxide, [0007]
  • (ii) contacting at least a part of the alkylaryl hydroperoxide obtained in step (i) with an olefin in the presence of a catalyst to obtain a product stream comprising an oxirane compound and alkylaryl hydroxyl, [0008]
  • (iii) optionally reacting part of the alkylaryl hydroperoxide obtained in step (i) to obtain a mixture comprising (a) phenol, and (b)a ketone and/or aldehyde, and optionally (c) by-products, [0009]
  • (iv) separating oxirane compound from the product stream of step (ii)to obtain (a) a residual product stream and (b) oxirane, [0010]
  • (v) contacting at least a part of the residual product stream with hydrogen to obtain alkylaryl, wherein at least a part of said alkylaryl is recycled to step (i). [0011]
    • DETAILED DESCRIPTION OF THE INVENTION
  • Although ethylbenzene is the alkylaryl compound most widely used in the preparation of an oxirane compound at present, it has been found that process step (i) can be carried out at higher conversion and higher selectivity if the alkylaryl compound employed is an alkylbenzene in which the alkyl substituent is a branched alkyl substituent comprising from 3 to 10 carbon atoms. A more preferred alkylaryl compound contains 1 or 2 alkyl substituents. An alkylaryl compound containing several substituents has the advantage that it can contain several hydroperoxide groups. However, in view of potential side-reactions, it is preferred that there are no more than 3 substituents, more preferably no more than 2 substituents. Most preferably, the alkylaryl compound is cumene and/or di(iso-propyl)benzene. Although mixtures of different alkylaryl compounds can be employed, a single type of compound is preferred in order to be able to optimise the process conditions for this specific compound. [0012]
  • The oxidation of the alkylaryl can be carried out by any suitable process known in the art. The oxidation can be carried out in the liquid phase in the presence of a diluent. This diluent is preferably a compound which is liquid under the reaction conditions and does not react with the starting materials and product obtained. However, the diluent can also be a compound necessarily present during the reaction. For example, if the alkylaryl is cumene the diluent can be cumene as well. [0013]
  • The product obtained in step (i) can be used as such in step (ii), or it can be preferred to separate off some compounds, or it can be preferred to only use part of the product obtained and to use another part in another process. [0014]
  • Preferably, part of the product of step (i) is used in step (iii), namely reaction of the alkylaryl hydroperoxide to obtain phenol and ketone and/or aldehyde. The phenol obtained can contain substituents. The reaction of the alkylaryl hydroperoxide can be attained by contacting the alkylaryl hydroperoxide with a catalyst such as an acidic catalyst. As non-limiting illustrative examples of the acidic catalysts which can be used include, but not limited to, sulphuric acid, hydrochloric acid, perchloric acid, sulphur dioxide and sulphur trioxide; organic acids such as benzenesulphonic acid, p-toluenesulphonic acid, cresolsulphonic acid and chloroacetic acid; solid acids such as silica-alumina, alumina and acidic ion exchange resins; heteropolyacids such as tungstosilicic acid, tungstophosphoric acid and molybdophosphosphoric acid. Preferably, sulphuric acid and/or cresolsulphonic acid are used. The amount of catalyst to be used is usually in the range of from about 0.0001 to 1% wt, based on the reaction mixture to be treated. The reaction temperature is usually in the range of from 30 to 150° C. [0015]
  • The alkylaryl hydroperoxide can be subject to the reaction after other compounds have been separated off from the reaction product of step (i). However, it is preferred to subject part of the reaction product of step (i) directly to the reaction of step (iii). [0016]
  • The reaction in step (iii) usually produces by-products. In order to further increase the conversion into the desired products phenol and ketone and/or aldehyde, the desired products can be separated from the reaction product of step (iii) and at least part of the by-products obtained in step (iii) are sent to step (v). Product to be hydrogenated can be separated off and subsequently subjected to hydrogenation, or part or all of the remaining reaction product can be directly subjected to hydrogenation. [0017]
  • If part of the alkylaryl hydroperoxide is converted into phenol and ketone and/or aldehyde, it is preferred that the alkylaryl is cumene as this gives phenol and acetone in step (iii). [0018]
  • In step (ii), alkylaryl hydroperoxide obtained in step (i) is contacted with olefin in the presence of a catalyst to obtain an oxirane compound and hydroxyalkylaryl. A catalyst which can suitably used in such process comprises titanium on silica and/or silicate. A preferred catalyst is described in EP-B-345856, the disclosure of which is herein incorporated by reference. The reaction generally proceeds at moderate temperatures and pressures, in particular at temperatures in the range of from 0 to 200° C., preferably in the range from 25 to 200° C. The precise pressure is not critical as long as it suffices to maintain the reaction mixture in a liquid condition. Atmospheric pressure may be satisfactory. In general, pressures can be in the range of from about 1 to about 100×10[0019] 5 N/m2.
  • The olefin to be used in the process in the present invention depends on the oxirane compound to be prepared. Preferably, the olefin contains from 2 to 10 carbon atoms, more preferably from 2 to 8 carbon atoms. Most preferably, the olefin is propene. [0020]
  • At the conclusion of the epoxidation reaction, the liquid mixture comprising the desired products is separated from the catalyst. The oxirane compound can then be separated from the reaction product in any way known to be suitable to someone skilled in the art. The liquid reaction product may be worked up by fractional distillation, selective extraction and/or filtration. The catalyst, any solvent which might be present and any unreacted olefin or alkylaryl hydroperoxide may be recycled for further utilization. [0021]
  • Process step (ii) can be carried out with the catalyst in the form of a slurry, of a moving bed or a fluidized bed. However, a fixed bed is preferred for large-scale industrial application. The process may be carried out in a batch-wise manner, semi-continuously or continuously. The liquid containing the reactants may then be passed through the catalyst bed, so that the effluent from the reaction zone is substantially free from catalyst. [0022]
  • Subsequently, at least part of the reaction product stream containing hydroxyalkylaryl from which an oxirane compound has been separated off, is subjected to hydrogenation. A hydrogenation treatment which can be used comprises contacting reaction product with hydrogen at a temperature of from about 140 to about 330° C., preferably of from about 180 to about 320° C., and a pressure of from about 0.1 to about 10×10[0023] 5 N/m2. The hydrogenation treatment is preferably carried out in the presence of a hydrogenation catalyst. Generally, the hydrogenation catalyst will contain a metal on a solid carrier which metal catalyses hydrogenation. Preferred catalysts are catalysts containing from 0.5 to 5% wt of metal or a metal compound on a carrier. Preferably, the metal present as metal or metal compound is one or more metal chosen from Group 1b, 2b, 3a, 4a, 4b, 5b, 6b, 7b and 8 of the Periodic Table of the Elements described in the Handbook of Chemistry and Physics, 63rd Edition. Catalysts which have been found to be suitable are the catalysts described in U.S. Pat. No. 5,475,159, the description of which is herein incorporated by reference. Further preferred catalyst are described in PCT/EP99/04275, the description of which is herein incorporated by reference.
  • After hydrogenation, the hydrogenated product can be recycled in total or in part. If only part of the hydrogenated product is recycled, the desired fraction can be separated off in any way suitable to someone skilled in the art. [0024]
  • The process according to the present invention is illustrated by the following Examples.[0025]
    • EXAMPLE 1
  • The epoxidation catalyst was a catalyst containing titanium on silica which was prepared as described in the Example according to the teaching of EP-A-345856, the description of which is herein incorporated by reference. [0026]
  • The hydrogenation catalyst was a catalyst containing copper, zinc and zirconium prepared according to Example 3 of U.S. Pat No. 5,475,159, incorporated herein by reference. [0027]
  • Fresh cumene and recycled cumene were fed to a reactor. During 8 hours, air was bubbled in at the bottom of the reactor and left at the top of the reactor. The reactor was cooled during the reaction due to the exothermic nature of the oxidation. The reaction product obtained contained 28% wt of cumene hydroperoxide, 70% wt of cumene and 2% wt of further compounds. [0028]
  • A reaction mixture containing about 6 mole of 1-octene per mole of cumene hydroperoxide was fed to a reactor containing the fresh epoxidation catalyst described above at a temperature of 40° C. Octene oxide was separated off. It was found that 55% wt of 1-octene was converted into octene oxide. [0029]
  • A mixture containing 17% wt of 2-phenyl-2-propanol and 83% wt of cumene was contacted with hydrogen in the presence of the hydrogenation catalyst described above at a temperature of 140° C. and a pressure of 20×10[0030] 5 N/m2 during 2 hours. The product obtained contained 10% wt of 2-phenyl-2-propanol, 86% wt of cumene, and 4% wt of alpha methyl styrene.
    • EXAMPLE 2
  • A mixture containing 17% wt of 2-phenyl-2-propanol and 83% wt of cumene was contacted with hydrogen in the presence of a hydrogenation catalyst comprising 5% wt of palladium on a charcoal carrier, at a temperature of 225° C. and a pressure of 20×10[0031] 5 N/m2 during 2 hours. The product obtained contained 1 % wt of 2-phenyl-2-propanol, 94% wt of cumene, 3% wt of i-propylcyclohexane and 2% wt of further compounds.
    • EXAMPLE 3
  • The experiment of Example 2 was repeated with the difference that the temperature was 280° C. The product obtained contained no 2-phenyl-2-propanol, 89 % wt of cumene, 10% wt of i-propylcyclohexane and 1 % wt of further compounds. [0032]
    • EXAMPLE 4
  • Fresh ethylbenzene and recycled ethylbenzene were fed to a reactor. During 8 hours, air was bubbled in at the bottom of the reactor and left at the top of the reactor. The reactor was cooled during the reaction due to the exothermic nature of the oxidation. The reaction product obtained contained 10 % wt of ethyl benzene hydroperoxide, 88% wt of ethylbenzene and 2% wt of further compounds. [0033]
  • A reaction mixture containing about 6 mole of 1-octene per mole of ethylbenzene hydroperoxide was fed to a reactor containing the fresh epoxidation catalyst described in Example 1 at a temperature of 40° C. Octene oxide was separated off. It was found that 41% wt of 1-octene was converted into octene oxide. [0034]

Claims (6)

What is claimed is:
1. A process for preparing oxirane compounds, which process comprises: comprises:
(i) oxidizing an alkylaryl to obtain a stream comprising alkylaryl hydroperoxide,
(ii) contacting at least part of the alkylaryl hydroperoxide obtained in step (i) with an olefin in the presence of a catalyst to obtain a product stream comprising an oxirane compound and alkylaryl hydroxyl,
(iii) optionally reacting part of the alkylaryl hydroperoxide obtained in step (i) to obtain a mixture comprising (a) phenol, and (b) a ketone and/or aldehyde, and (c) optionally by-products,
(iv) separating oxirane compound from the product stream of step (ii) to obtain (a) a residual product stream and (b) oxirane, and
(v) contacting at least a part of the residual product stream with hydrogen to obtain alkylaryl, wherein at least a part of said alkylaryl is recycled to step (i).
2. The process according to claim 1, in which process the alkylaryl compound is an alkylbenzene in which the alkyl substituent is a branched alkyl substituent comprising from 3 to 10 carbon atoms.
3. The process according to claim 1, in which process the alkylaryl compound is selected from the group comprising (i)cumene, (ii) di(iso-propyl)benzene, and (iii) a mixture of cumene and di(iso-propyl)benzene.
4. The process according to claim 1, in which at least a part of the by-products (c)obtained in step (iii) are sent to step (v).
5. The process according to claim 1, in which in step (ii) alkylaryl hydroperoxide is contacted with olefin at a temperature in the range of from about 0 to about 200° C., and a pressure in the range of from about 1 to about 100×105 N/m2 in the presence of a catalyst comprising titanium on silica and/or silicate.
6. The process according to claim 1, in which the hydrogenation of in process step (v) is carried out a temperature of from about 140 to about 330° C., and a pressure of from about 0.1 to about 50×105 N/m2 in the presence of a hydrogenation catalyst.
US09/736,522 2000-12-13 2000-12-13 Preparation of oxirane compounds Expired - Lifetime US6455712B1 (en)

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US09/736,522 US6455712B1 (en) 2000-12-13 2000-12-13 Preparation of oxirane compounds
JP2002549657A JP2004517842A (en) 2000-12-13 2001-12-13 Method for preparing oxirane compounds
CNB01820578XA CN1213041C (en) 2000-12-13 2001-12-13 Prepn. of oxirane compounds
EP01270532A EP1347962A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
CNB018205771A CN1232516C (en) 2000-12-13 2001-12-13 Prepn. of oxirane compounds
KR10-2003-7007769A KR20030059334A (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
BR0116101-6A BR0116101A (en) 2000-12-13 2001-12-13 Process for the preparation of oxirane compounds
AU2002216112A AU2002216112B2 (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
RU2003121243/04A RU2282624C2 (en) 2000-12-13 2001-12-13 Oxirane compounds preparing
PCT/EP2001/014751 WO2002048127A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
PCT/EP2001/014748 WO2002048125A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
RU2003121244/04A RU2282625C2 (en) 2000-12-13 2001-12-13 Oxirane compounds preparing
AU3843302A AU3843302A (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
RU2003121245/04A RU2282623C2 (en) 2000-12-13 2001-12-13 Method for preparing compounds of oxirane, phenol, ketones and/or aldehydes
BR0116099-0A BR0116099A (en) 2000-12-13 2001-12-13 Process for the preparation of oxirane, phenol and ketone compounds and / or aldehydes
KR10-2003-7007771A KR20030075151A (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
TW090130947A TWI248929B (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
JP2002549656A JP2004517841A (en) 2000-12-13 2001-12-13 Method for preparing oxirane compounds
EP01986878A EP1343776A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
TW090130929A TWI247743B (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
AU2002217114A AU2002217114B2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
JP2002549658A JP2004525870A (en) 2000-12-13 2001-12-13 Method for preparing oxirane compounds
KR1020037007770A KR100843780B1 (en) 2000-12-13 2001-12-13 How to prepare an oxirane compound
AU1711402A AU1711402A (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
BR0116100-8A BR0116100A (en) 2000-12-13 2001-12-13 Process for the preparation of oxirane compounds
PCT/EP2001/014750 WO2002048126A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
TW090130928A TW593298B (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
AU2002238433A AU2002238433B2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds
AU1611202A AU1611202A (en) 2000-12-13 2001-12-13 Preparation of oxirane compounds
CNB018205909A CN1243743C (en) 2000-12-13 2001-12-13 The preparation method of epoxy compound
EP01270533A EP1366031A2 (en) 2000-12-13 2001-12-13 Process for preparing oxirane compounds

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Families Citing this family (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10105527A1 (en) * 2001-02-07 2002-08-08 Basf Ag Process for the production of an epoxy
BRPI0308966B8 (en) 2002-04-03 2016-05-17 Vaelinge Innovation Ab floor board
US6844454B2 (en) 2002-04-12 2005-01-18 Shell Oil Company Process
US7125819B2 (en) 2002-12-02 2006-10-24 Shell Oil Company Catalyst preparation
EP1644304A2 (en) * 2003-06-30 2006-04-12 Shell International Research Maatschappij B.V. Process for producing alkylbenzene
US7193093B2 (en) * 2003-06-30 2007-03-20 Shell Oil Company Process for producing alkylene oxide
US7358411B2 (en) * 2003-06-30 2008-04-15 Shell Oil Company Hydrocracking of diphenylalkanes
KR20060081702A (en) * 2003-08-19 2006-07-13 셀 인터나쵸나아레 레사아치 마아츠샤피 비이부이 Method for preparing alkylene oxide
PL1936068T3 (en) 2004-10-22 2012-07-31 Vaelinge Innovation Ab A method of providing floor panels with a mechanical locking system
DE202004021867U1 (en) 2004-10-22 2011-12-27 Välinge Innovation AB Mechanical lock for floor panels
US7841144B2 (en) 2005-03-30 2010-11-30 Valinge Innovation Ab Mechanical locking system for panels and method of installing same
US7454875B2 (en) 2004-10-22 2008-11-25 Valinge Aluminium Ab Mechanical locking system for floor panels
KR100589063B1 (en) * 2004-12-15 2006-06-12 현인기술 주식회사 Head massager structure
US8061104B2 (en) 2005-05-20 2011-11-22 Valinge Innovation Ab Mechanical locking system for floor panels
RU2008147409A (en) 2006-05-02 2010-06-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. (NL) TITANIUM CATALYST, METHOD OF ITS PRODUCTION AND USE IN EPOXIDATION REACTIONS
SE533410C2 (en) 2006-07-11 2010-09-14 Vaelinge Innovation Ab Floor panels with mechanical locking systems with a flexible and slidable tongue as well as heavy therefore
US8689512B2 (en) 2006-11-15 2014-04-08 Valinge Innovation Ab Mechanical locking of floor panels with vertical folding
SE531111C2 (en) 2006-12-08 2008-12-23 Vaelinge Innovation Ab Mechanical locking of floor panels
US8499521B2 (en) 2007-11-07 2013-08-06 Valinge Innovation Ab Mechanical locking of floor panels with vertical snap folding and an installation method to connect such panels
EP3597837B8 (en) 2008-01-31 2021-08-04 Välinge Innovation AB Method to produce a mechanical locking of building panels
EP2304126B1 (en) 2008-05-15 2019-07-03 Välinge Innovation AB Floor panels with a mechanical locking system activated by a magnetic field
BR212012016569Y1 (en) 2010-01-12 2020-05-19 Välinge Innovation AB set of floor panels that are mechanically connectable to each other along a pair of adjacent edges
EP2531667B1 (en) 2010-02-04 2020-08-26 Välinge Innovation AB Mechanical locking system for floor panels and corresponding tongue
EP2558658B1 (en) 2010-04-15 2018-11-21 Unilin, BVBA Floor panel assembly
US8664412B2 (en) 2010-07-19 2014-03-04 Shell Oil Company Epoxidation process
UA109938C2 (en) 2011-05-06 2015-10-26 MECHANICAL LOCKING SYSTEM FOR CONSTRUCTION PANELS
UA114715C2 (en) 2011-07-05 2017-07-25 Сералок Інновейшн Аб Mechanical locking of floor panels with a glued tongue
US9725912B2 (en) 2011-07-11 2017-08-08 Ceraloc Innovation Ab Mechanical locking system for floor panels
US8650826B2 (en) 2011-07-19 2014-02-18 Valinge Flooring Technology Ab Mechanical locking system for floor panels
US8857126B2 (en) 2011-08-15 2014-10-14 Valinge Flooring Technology Ab Mechanical locking system for floor panels
US9216541B2 (en) 2012-04-04 2015-12-22 Valinge Innovation Ab Method for producing a mechanical locking system for building panels
EP3613920B1 (en) 2012-11-22 2024-01-31 Ceraloc Innovation AB Mechanical locking system for floor panels
EP4166731B1 (en) 2013-06-27 2025-06-11 Välinge Innovation AB Set of panels with a mechanical locking system
US10246883B2 (en) 2014-05-14 2019-04-02 Valinge Innovation Ab Building panel with a mechanical locking system
WO2015174914A1 (en) 2014-05-14 2015-11-19 Välinge Innovation AB Building panel with a mechanical locking system
EP3023402A1 (en) 2014-11-20 2016-05-25 Shell Internationale Research Maatschappij B.V. Improvements relating to hydrogenolysis of phenyl alcohols
EA033977B1 (en) 2014-11-27 2019-12-16 Велинге Инновейшн Аб Mechanical locking system for floor panels
WO2017080962A1 (en) 2015-11-09 2017-05-18 Shell Internationale Research Maatschappij B.V. Catalyst preparation
WO2018148610A1 (en) * 2017-02-10 2018-08-16 Adimab, Llc Proteins binding psma, nkg2d and cd16

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3350422A (en) 1966-02-01 1967-10-31 Halcon International Inc Catalytic epoxidation of an olefinically unsaturated compound using an organic hydroperoxide as an epoxidizing agent
US4400558A (en) * 1981-04-17 1983-08-23 Atlantic Richfield Company Recovery of 2-phenylethanol
GB8813484D0 (en) * 1988-06-08 1988-07-13 Shell Int Research Process for preparation of oxirane compound
US5017729A (en) * 1988-09-30 1991-05-21 Mitsui Petrochemical Industries, Ltd. Phenol preparation process and propylene recovery therefrom
RU1839668C (en) * 1988-11-28 1993-12-30 МИЦУИ ПЕТРОКЕМИКАЛ ИНДАСТРИЗ, Лтд (JP) Method of phenol synthesis
US5371305A (en) * 1992-12-31 1994-12-06 Hercules Incorporated Process for producing phenol from cumene
JPH08510563A (en) 1993-03-15 1996-11-05 ミネソタ・マイニング・アンド・マニュファクチュアリング・カンパニー Ballasted leuco dyes and photothermographic elements containing same
US5475159A (en) 1994-11-07 1995-12-12 Shell Oil Company Process for the direct hydrogenation of methyl esters
US5723637A (en) * 1995-12-06 1998-03-03 Sumitomo Chemical Company, Limited Process for producing propylene oxide
US6011162A (en) * 1997-05-05 2000-01-04 Arco Chemical Technology, L.P. Epoxidation process using improved heterogeneous catalyst composition
JPH11140068A (en) * 1997-11-07 1999-05-25 Sumitomo Chem Co Ltd Method for producing propylene oxide
RU2140896C1 (en) * 1998-08-17 1999-11-10 ОАО "Нижнекамскнефтехим" Method of purification of recovery ethylbenzene from low-boiling hydrocarbon fraction in production of propylene oxide and styrene
JP2001031662A (en) 1999-07-14 2001-02-06 Sumitomo Chem Co Ltd Method for producing propylene oxide
JP2001270879A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Process for producing oxirane compounds
JP2001270872A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Method for producing propylene oxide
JP2001270876A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Method for producing propylene oxide
JP2001270877A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Method for producing propylene oxide
JP2001270874A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Method for producing propylene oxide
JP2001270871A (en) 2000-03-24 2001-10-02 Sumitomo Chem Co Ltd Process for producing oxirane compounds

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KR20030075151A (en) 2003-09-22
CN1481374A (en) 2004-03-10
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TW593298B (en) 2004-06-21
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